1. Industrial Applicable Field
The invention relates to a method for producing an axial asymmetric aminophosphine compound, an intermediate for producing the same, a method for producing a complex of a metal such as ruthenium, rhodium, iridium or nickel and the compound, and a catalyst for asymmetric hydrogenation or carbon-carbon bond formation using the complex.
2. Related Art Statement
There has been a number of reports describing complexes of transition metal elements available for asymmetric synthesis such as asymmetric hydrogenation, asymmetric isomerization or asymmetric hydrosilylation. Particularly, a complex of a transition metal element, such as ruthenium, rhodium, iridium, palladium or the like, with an optically active tertiary phosphine compound as its ligand has excellent properties as a catalyst for asymmetric synthesis.
Phosphine compounds with various chemical structures have been developed for further improving their performances as the catalysts (xe2x80x9cChemical Reviewxe2x80x9d 32, xe2x80x9cchemistry of organic metal complexesxe2x80x9d, page 237 to 238, edited by Japan Chemical Society, 1982) (xe2x80x9cAsymmetric Catalysis in Organic Synthesisxe2x80x9d Noyori Yoshiharu, A Wiley-Interscience Publication). 2,2xe2x80x2-Bis(diphenylphosphino)-1,1xe2x80x2-binaphthyl (referred to as xe2x80x9cBINAPxe2x80x9d below) is one of optically active phosphines having excellent properties. A complex of rhodium with xe2x80x9cBINAPxe2x80x9d is described in Japanese Patent Laid-Open publication xe2x80x9cKokaixe2x80x9d 61973/1980 and a complex of ruthenium with xe2x80x9cBINAPxe2x80x9d is described in Japanese Patent Laid-Open publication xe2x80x9cKokaixe2x80x9d 6390/1986. Further, a complex having 2,2xe2x80x2-bis[di(p-tolyl)phosphino]-1,1xe2x80x2-binapthyl (referred to as xe2x80x9cp-Tol-BINAPxe2x80x9d below) as its ligand is described in Japanese Patent Laid-Open publication xe2x80x9cKokaixe2x80x9d 199898/1985 (rhodium) or 63690/1986 (ruthenium). These complexes are reported to provide good results for asymmetric hydrogenation and asymmetric isomerization. Further, Japanese Patent Laid-Open publication xe2x80x9cKokaixe2x80x9d 255090/1991 discloses ruthenium complex of 2,2xe2x80x2-bis(di-3,5-dialkylphenyl)phosphino)-1,1xe2x80x2-binapthyl to have superior performance as a catalyst for asymmetric hydrogenation of, xcex2-ketoesters. Further, palladium complexes of aminophosphine compounds have been used for asymmetric hydrosilylation. For example, a palladium complex having as its ligand an optically active aminophosphine compound with ferrocene bone structure is effective as a catalyst for asymmetric hydrosilylation of a conjugated diene compound with trichlorosilane (Tetrahedron Lett., Asymmetry, 1, 151(1990)). A palladium complex having an aminophosphine compound with N-sulfonyl group as its ligand is effective as a catalyst for hydrosilylation of styrene with chlorosilane (Chem. Lett. 999(1990)). Further, a nickel complex having as its ligand an aminophosphine compound having ferrocene bone structure is effective as a catalyst for asymmetric cross-coupling reaction of 1-phenylethylmagnesiuua chloride and vinyl chloride (J. Am. Chem. Soc. 104, 180(1982)). However, the above catalysts do not necessarily have sufficient chemical selectivity, enantioselectivity and catalytic activity depending on the reaction type or the substrate, leading to the needs for improving these kinds of catalysts.
Further, a phosphine compound 7 having a nitrogen atom in its molecule has been synthesized using an optically active 2-amino-2xe2x80x2-hydroxybinaphthyl as a starting material, according to the method described in a publication (J. Org. Chem. 63, 7738 (1988)). Moreover, an optically active 2-amino-2xe2x80x2-hydroxybinaphthyl has been obtained by the oxidative addition of 2-aminonaphthalene and 2-hydroxynaphthalene in the presence of sparteine or phenethylamine, or by the optical resolution of racemic mixture of 2-amino-2xe2x80x2-hydroxybinaphthyl. However, 2-aminonaphthalene is now difficult to obtain in the market due to its carcinogenicity and the above synthetic route using it is not desirable in the viewpoint of environmental protection. 
The inventive process utilizes safe 1,1xe2x80x2-bi-2-naphthol as the starting material for synthesizing a ligand composed of a phosphine having a nitrogen atom within its molecule, thus avoiding the above problems. Further, according to the examples in the above publication, as shown in the following scheme 1, the compound 8 is subjected to a substitution reaction of its allyl position with malonic ester in the presence of a catalyst containing palladium (so called xe2x80x9cTsuji reactionxe2x80x9d). 
All the examples in the above publication is performed according to the above reaction scheme. Moreover, all the ligands used in the examples are selected from the following phosphine compounds 11, 12, 13 and 14, each having a dialkylamino group. The following free aminophosphine 15 is used only as a starting material and not used as a ligand throughout the examples. 
The object of the invention is to provide a metal complex which has a novel aminophosphine compound as its ligand and superior characteristics as a catalyst (chemical selectivity, enantioselectivity, catalytic activity) for asymmetric synthesis, especially asymmetric carbon-carbon bond formation and asymmetric hydrogenation.
The inventors have extensively studied many phosphine compounds to give a solution to the above problems and finally found that a complex containing a transition metal and an axially asymmetric and optically active aminophosphine compound having a nitrogen atom in its molecule, that is, 2-amino-2xe2x80x2-diarylphosphino-1-1xe2x80x2-binaphthyl (referred to as xe2x80x9cMAPxe2x80x9d below), is effective for asymmetric hydrogenation. The compound is an aminophosphine compound having binaphthyl group whose one naphthalene ring is connected to an amino group or a substituted amino group and the other naphthalene ring is connected to a diarylphosphino group. The inventors further found that the complex shows superior catalytic activity and enantioselectivity for asymmetric carbon-carbon bond formation.
The invention therefore provides a method for producing 2-amino-2xe2x80x2-diarylphosphino-1-1xe2x80x2-binaphthyl represented by the following formula (1-1) 
(referred to as xe2x80x9cSMAPxe2x80x9d below), or formula (1-2) 
(referred to as xe2x80x9cCMAPxe2x80x9d below), or formula (1-3) 
(referred to as xe2x80x9cSUMAPxe2x80x9d below). The invention further provides a complex of a transition metal having as its ligand one of the aminophosphine compounds represented by the following formulae (1-1), (1-2) and (1-3), and a method for producing the complex. Formula (1-1) 
(In the formula, each Ar represents an aryl group (preferably phenyl group) which may be substituted with a halogen atom, a lower alkyl group having 1 to 4 carbon atom or an alkoxy group, with both Ar""s being same or different with each other. R1 and R2 represent hydrogen atom, a cycloalkyl group having 5 to 7 carbon atoms, or an alkyl group having 1 to 6 carbon atom which may be substituted with a halogen atom, a lower alkoxy group or phenyl group, with R1 and R1 being same or different with each other.) The cycloalkyl group having 5 to 7 carbon atoms for R1 and R2 includes cyclopentyl group and cyclohexyl group. The alkyl group having 1 to 6 carbon atom which may be substituted with a halogen atom, a lower alkoxy group or phenyl group for R1 and R2 includes methyl, ethyl, butyl, hexyl, isopropyl, tert-butyl, fluoromethyl, 2,2,2-trifluoroethyl, 3,3,4,4,5,5,6,6,6-nonafluorohexyl, methoxymethyl, methoxyethoxymethyl, methoxypropyl, methoxybutyl, ethoxyethoxymethyl, methoxypropoxymethyl, butoxymethyl, benzyl, diphenylmethyl and phenylpropyl groups or the like, and may preferably be an alkyl group having 1 to 4 carbon atoms, methoxyethyl group or methoxyethoxymethyl group. Further, in the formula (1-1), Ar represents an aryl group (preferably phenyl group) which may be substituted with a halogen atom, a lower alkyl group having 1 to 4 carbon atom or an alkoxy group, and may preferably be unsubstituted phenyl group, p-tolyl group and 3,5-methylphenyl group. 
(In the formula, each Ar represents an aryl group (preferably phenyl group) which may be substituted with a halogen atom, a lower alkyl group having 1 to 4 carbon atom or an alkoxy group, with both Ar""s being same or different with each other. R3 represents a cycloalkyl group having 5 to 7 carbon atoms, or an alkyl group having 1 to 6 carbon atom which may be substituted with a halogen atom, a lower alkoxy group or phenyl group, substituted or unsubstituted phenyl group, or a lower alkoxy group.). The cycloalkyl group having 5 to 7 carbon atoms for R3 includes cyclopentyl group, cyclohexyl group or the like. The alkyl group having 1 to 6 carbon atom which may be substituted with a hydrogen atom, a lower alkoxy group or phenyl group includes methyl, ethyl, butyl, hexyl, isopropyl, tert-butyl, fluoromethyl, 2,2,2-trifluoroethyl, 3,3,4,4,5,5,6,6,6-nonafluorohexyl, methoxymethyl, methoxyethoxymethyl, methoxypropyl, methoxybutyl, ethoxyethoxymethyl, methoxypropoxymethyl, butoxymethyl, benzyl, diphenylmethyl and phenylpropyl groups or the like, and may preferably be an alkyl group having 1 to 4 carbon atom or benzyl group. R3 may be unsubstituted phenyl group or phenyl group substituted with a halogen atom, a lower alkyl group having 1 to 4 carbon atom or an alkoxy group, and may preferably be unsubstituted phenyl group, p-tolyl group or 3,5-dimethylphenyl group. The lower alkoxy group for R3 includes methoxy, ethoxy, propoxy, butoxy, isopropoxy, tert-butoxy, benzyloxy groups or the like, and may preferably be methoxy group, tert-butoxy group and benzyloxy group. Further in the formula (1-2), Ar represents phenyl group which may be substituted with a halogen atom, a lower alkyl group having 1 to 4 carbon atom or an alkoxy group, and may preferably be unsubstituted phenyl group, p-tolyl group or 3,5-dimethylphenyl group. 
(In the formula, each Ar represents an aryl group (preferably phenyl group) which may be substituted with a halogen atom, a lower alkyl group having 1 to 4 carbon atom or an alkoxy group, with both Ar""s being same or different with each other. R4 represents a cycloalkyl group having 5 to 7 carbon atoms, or an alkyl group having 1 to 6 carbon atom which may be substituted with a hydrogen atom, a lower alkoxy group or phenyl group, or substituted or unsubstituted phenyl group.). The cycloalkyl group having 5 to 7 carbon atoms for R4 includes cyclopentyl group, cyclohexyl group or the like. The alkyl group having 1 to 6 carbon atom, which may be substituted with a hydrogen atom, a lower alkoxy group or phenyl group, includes methyl, ethyl, butyl, hexyl, isopropyl, tert-butyl, fluoromethyl, 2,2,2-trifluoroethyl, 3,3,4,4,5,5,6,6,6-nonafluorohexyl, methoxymethyl, methoxyethoxymethyl, methoxypropyl, methoxybutyl, ethoxyethoxymethyl, methoxypropoxymethyl, butoxymethyl, benzyl, diphenylmethyl and phenylpropyl groups or the like, and may preferably be an alkyl group having 1 to 4 carbon atom. R4 may be unsubstituted phenyl group or phenyl group substituted with a halogen atom, a lower alkyl group having 1 to 4 carbon atom or an alkoxy group, and may preferably be unsubstituted phenyl group, p-tolyl group or 3,5-dimethylphenyl group. Further in the formula (1-3), Ar represents an aryl group (preferably phenyl group) which may be substituted with a halogen atom, a lower alkyl group having 1 to 4 carbon atom and an alkoxy group, and may preferably be unsubstituted phenyl group, p-tolyl group or 3,5-dimethylphenyl group.
Aminophosphine compounds as important intermediates for synthesizing the inventive aminophosphine compounds (1-1). (1-2) and (1-3) are represented by the following formula (1-1-1) 
or the formula (1-3-1) 
or the formula (5). 
(In the formula, each Ar represents an aryl group (preferably phenyl group) which may be substituted with a halogen atom, a lower alkyl group having 1 to 4 carbon atom or an alkoxy group, with both Ar""s being same or different with each other. R1 and R2 represent hydrogen atom, a cycloalkyl group having 5 to 7 carbon atoms, or an alkyl group having 1 to 6 carbon atom which may be substituted with a halogen atom, a lower alkoxy group or phenyl group, with R1 and R2 being same or different with each other.) The cycloalkyl group having 5 to 7 carbon atoms for R1 and R2 includes cyclopentyl group, cyclohexyl group or the like. The alkyl group having 1 to 6 carbon atom for R1 and R2 which may be substituted with a halogen atom, a lower alkoxy group or phenyl group, includes methyl, ethyl, butyl, hexyl, isopropyl, tert-butyl, fluoromethyl, 2,2,2-trifluoroethyl, 3,3,4,4,5,5,6,6,6-nonafluorohexyl, methoxymethyl, methoxyethoxymethyl, methoxypropyl, methoxybutyl, ethoxyethoxymethyl, methoxypropoxymethyl, butoxymethyl, benzyl, diphenylmethyl and phenylpropyl groups or the like, and may preferably be an alkyl group having 1 to 4 carbon atom, methoxyethyl group and methoxyethoxymethyl group. Further, in the formula (1-1-1), Ar represents an aryl group (preferably phenyl group) which may be substituted with a halogen atom, a lower alkyl group having 1 to 4 carbon atom or an alkoxy group, and may preferably be unsubstituted phenyl group, p-tolyl group or 3,5-methylphenyl group. 
(In the formula, each Ar represents an aryl group (preferably phenyl group) which may be substituted with a halogen atom, a lower alkyl group having 1 to 4 carbon atom or an alkoxy group, with both Ar""s being same or different with each other. R3 represents a cycloalkyl group having 5 to 7 carbon atoms, or an alkyl group having 1 to 6 carbon atoms which may be substituted with a halogen atom, a lower alkoxy group or phenyl group, substituted or unsubstituted phenyl group, or a lower alkoxy group.). The cycloalkyl group having 5 to 7 carbon atoms for R3 includes cyclopentyl group, cyclohexyl group or the like. The alkyl group having 1 to 6 carbon atom which may be substituted with a hydrogen atom, a lower alkoxy group or phenyl group includes methyl, ethyl, butyl, hexyl, isopropyl, tert-butyl, fluoromethyl, 2,2,2-trifluoroethyl, 3,3,4,4,5,5,6,6,6-nonafluorohexyl, methoxymethyl, methoxyethoxymethyl, methoxypropyl, methoxybutyl,, ethoxyethoxymethyl, methoxypropoxymethyl, butoxymethyl, benzyl, diphenylmethyl or phenylpropyl groups or the like, and may preferably be an alkyl group having 1 to 4 carbon atom or benzyl group. R3 may be unsubstituted phenyl group or phenyl group substituted with a halogen atom, a lower alkyl group having 1 to 4 carbon atom or an alkoxy group, may preferably be unsubstituted phenyl group, p-tolyl group or 3,5-dimethylphenyl group. The lower alkoxy group for R3 includes methoxy, ethoxy, propoxy, butoxy, isopropoxy, tert-butoxy, benzyloxy groups or the like, and may preferably be methoxy group, tert-butoxy group or benzyloxy group. Further in the formula (1-2-1), Ar represents an aryl group (preferably phenyl group) which may be substituted with a halogen atom, a lower alkyl group having 1 to 4 carbon atom or an alkoxy group, and may preferably be unsubstituted phenyl group, p-tolyl group or 3,5-dimethylphenyl group. 
(In the formula, each Ar represents an aryl group (preferably phenyl group) which may be substituted with a halogen atom, a lower alkyl group having 1 to 4 carbon atom or an alkoxy group, with both Ar""s being same or different with each other. R4 represents a cycloalkyl group having 5 to 7 carbon atoms, or an alkyl group having 1 to 6 carbon atom which may be substituted with a hydrogen atom, a lower alkoxy group or phenyl group, or substituted or unsubstituted phenyl group.). The cycloalkyl group having 5 to 7 carbon atoms for R4 includes cyclopentyl group, cyclohexyl group or the like. The alkyl group having 1 to 6 carbon atoms, which may be substituted with a hydrogen atom, a lower alkoxy group or phenyl group, includes methyl, ethyl, butyl, hexyl, isopropyl, tert-butyl, fluoromethyl, 2,2,2-trifluoroethyl, 3,3,4,4,5,5,6,6,6-nonafluorohexyl, methoxymethyl, methoxyethoxymethyl, methoxypropyl, methoxybutyl, ethoxyethoxymethyl, methoxypropoxymethyl, butoxymethyl, benzyl, diphenylmethyl and phenylpropyl groups or the like, and may preferably be an alkyl group having 1 to 4 carbon atom. R4 may be unsubstituted phenyl group or phenyl group substituted with a halogen atom, a lower alkyl group having 1 to 4 carbon atom or an alkoxy group, and may preferably be unsubstituted phenyl group, p-tolyl group or 3,5-dimethylphenyl group. Further in the formula (1-3-1), Ar represents an aryl group (preferably phenyl group) which may be substituted with a halogen atom, a lower alkyl group having 1 to 4 carbon atom or an alkoxy group, and may preferably be unsubstituted phenyl group, p-tolyl group or 3,5-dimethylphenyl group. 
(In the formula, each Ar represents an aryl group (preferably phenyl group) which may be substituted with a halogen atom, a lower alkyl group having 1 to 4 carbon atom or an alkoxy group, with both Ar""s being same or different with each other.). Ar represents phenyl group which may be substituted with a halogen atom, a lower alkyl group having 1 to 4 carbon atom or an alkoxy group, and may preferably be unsubstituted phenyl group, p-tolyl group or 3,5-dimethylphenyl group.
The inventive 2-amino-2xe2x80x2-diarylphosphino-1-1xe2x80x2-binaphthyl (1-1), (1-2) or (1-3), 2-amino-2xe2x80x2-diarylphosphinyl-1,1xe2x80x2-binaphthyl(1-1-1), (1-2-1) or (1-3-1), or 2-carbamoyl-2!-diarylphosphinyl-1-1xe2x80x2-binapthyl (5) includes their optically active isomers, that is, (+) and (xe2x88x92) isomers. The invention includes the (+) isomer, (xe2x88x92) isomer, and the racemic mixture of each compound.
Although the invention will be described below further in detail mainly in reference to a compound (xe2x88x92)-SMAP represented by the following formula (1-1a ) as a particular example for simplicity, the invention is not limited to the particular example. 
The aminophosphine compound (1-1a) is an example of the inventive compound (1-1) wherein both Ar""s are phenyl groups and R1 and R2 are both hydrogen atoms. The compound (1-1a) may be synthesized by the following scheme 2. That is, alkaline hydrogen peroxide is reacted with known (+)-cyanophosphine oxide (4a) (Tetrahedron 50, 4293 (1994)) in DMSO to provide carbamoyl phosphine oxide (5a), which is then reacted with sodium methoxide and bromine in a mixture of methanol and dioxane to provide a methoxycarbonyl compound (1-2b-1). Carbamoyl phosphine oxide (5a) may be reacted with a metal alkoxide and bromine in an organic solvent to provide an alkoxycarbonylaminophosphine oxide compound being represented by the formula (1-2-1), in which each Ar is phenyl group which may be substituted with a halogen atom, a lower alkyl group or an alkoxy group with Ar""s being same or different with each other and R3 is a lower alkoxide group. The above metal alkoxide may be sodium methoxide, potassium methoxide, lithium methoxide, sodium ethoxide, potassium ethoxide, lithium ethoxide, sodium benzyloxide, sodium tert-butoxide, potassium tert-butoxide or the like.
The compound (1-2b-1) is then hydrolyzed by effecting a strong alkali in a solvent containing water, preferably by effecting potassium hydroxide in methanol containing water, to provide an aminophosphine oxide (1-1a-1). The compound (1-1a-1) may be reduced by trichlorosilane to provide a compound of the formula (1-1a), that is, (xe2x88x92)-SMAP), in which Ar is phenyl group and R1 and R2 are hydrogen atoms in the formula (1-1) with a high yield. (+)-SMAP may be produced by applying the similar scheme using (xe2x88x92)-cyanophosphine oxide.
When using racemic mixture of (+)-cyanophosphine oxide and (xe2x88x92)-cyanophosphine oxide as the starting material for producing the inventive compound (1-1a), its racemic mixture will be obtained. Therefore, the racemic mixture or only one of its optically active bodies may be produced according to the object of the resultant compound. 
One of the inventive compound (1-1) with R1 being methyl group and R2 being hydrogen atom, that is, the compound (1-1b), may be produced by treating the compound (1-2b-1) with a reducing agent, such as borane, according to the following scheme. 
The inventive compounds (1-1) with R1 being ethyl group and R 2being hydrogen atom (compound (1-1c)) and with R1 being benzyl group and R2 being hydrogen atom (compound (1-1d) may be produced by treating the compound (1-1a) with the corresponding acid chlorides, acetyl chloride or benzoyl chloride followed by the treatment with a reducing agent such as borane etc.
An acid chloride may be used for producing a compound represented by the formula (1-1) wherein R1 is a cycloalkyl group having 5 to 7 carbon atoms or an alkyl group which may be substituted with a halogen atom, a lower alkoxy group or phenyl group and R2 is hydrogen atom. Such acid chloride includes acetyl chloride, propionyl chloride, butyryl chloride, isobutyryl chloride, cyclohexanecarbonyl chloride, benzoyl chloride, acetyl bromide or the like. 
The compound (1-2b) (R3 is methoxy group in the formula (1-2))may be produced by reacting the compound (1-1a) with methyl chlorocarbonate. The compound of the formula (1-2) with R3 being a lower alkoxy group is produced by treating the compound (1-1a) with a chlorocarbonate ester or a oxydiformate diester. Such a chlorocarbonate ester, for producing the compound of the formula (1-2) with R3 being a lower alkoxy group, includes methyl chlorocarbonate, ethyl chlorocarbonate, propyl chlorocarbonate, butyl chlorocarbonate, isopropyl chlorocarbonate, benzyl chlorocarbonate or the like. Such a oxydiformate diester, for producing the compounds of the formula (1-2) with R3 being a lower alkoxy group, includes dimethyl oxydiformate, diethyl oxydiformate, dipropyl oxydiformate, dibutyl oxydiformate, diisopropyl oxydiformate, di-tert-butyl oxydiformate, dibenzyl oxydiformate or the like.
The compound (1-2a), which is the compound (1-2) with R3 being methyl group, may be produced by reacting the compound (1-1a) with acetyl chloride. Further, the compound (1-2c), which is the compound (1-2) with R3 being phenyl group, may be produced by reacting the compound (1-1a) with benzoyl chloride.
The acid chloride, for synthesizing the compound (1-2) with R3 being a cycloalkyl group having 5 to 7 carbon atoms, includes cyclopentylcarbonyl chloride, cyclohexylcarbonyl chloride or the like. The acid chloride, for producing the compound (1-2) with R3 being an alkyl group which may be substituted with a halogen atom, a lower alkoxy group or phenyl group, includes acetyl chloride, propionyl chloride, burylyl chloride, valeryl chloride, hexanoyl chloride, heptanoyl chloride, isobutyryl chloride, pyvaloyl chloride, fluoroacetyl chloride, 2,2,2-trifluoroacetyl chloride, 3,3,4,4,5,5,6,6,6-nonafluoroheptanoyl chloride, methoxyacetyl chloride, methoxyethoxyacetyl chloride, methoxybutyroyl chloride, methoxypentanoyl chloride, ethoxyethoxyacetyl chloride, methoxypropoxyacetyl chloride, butoxyacetyl chloride, benzoyl chloride, diphenyacetyl chloride, phenylbutyroyl chloride or the like, and may preferably be acetyl chloride, propionyl chloride, butyryl chloride, valeryl chloride or benzoyl chloride. The compounds (1-1b), (1-1c) and (1-1d) may be prepared by treating the corresponding compounds (1-2b), (1-2a) and (1-2c) with a reducing agent such as borane or the like. 
The compound (1-3a), which is the compound (1-3) with R4 being methyl group, may be prepared by treating the compound (1-1a-1) with methanesulfonyl chloride to provide the compound (1-3a-1), followed by the treatment with a reducing agent such as trichlorosilane or the like.
Further, the compound (1-3a) may be prepared by reacting the compound (1-1a) with methanesulfonyl chloride.
An organic sulfonyl chloride, used for producing the compound(1-3) with R4 being a cycloalkyl group having 5 to 7 carbon atoms, includes cyclopentanesulfonyl chloride, cyclohexanesulfonyl chloride or the like. An organic sulfonyl chloride, used for producing the compound(1-3) with R4 being an alkyl group having 1 to 6 carbon atom which may be substituted with a halogen atom, a lower alkoxy group or phenyl group, includes methanesulfonyl chloride, ethanesulfonyl chloride, butanesulfonyl chloride, hexanesulfonyl chloride, isopropylsulfonyl chloride, tert-butyl sulfonyl chloride, fluoromethanesulfonyl chloride, 2,2,2-trifluoroethanesulfonyl chloride, 3,3,4,4,5,5,6,6,6-nonafluorohexylsulfonyl chloride, methoxymethylsulfonyl chloride, methoxyethoxymethylsulfonyl chloride, methoxypropylsulfonyl chloride, methoxybutylsulfonyl chloride, ethoxyethoxymethylsulfonyl chloride, methoxypropoxymethylsulfonyl chloride, butoxymethylsulfonyl chloride, benzylsulfonyl chloride, diphenylmethylsulfonyl chloride, phenylpropylsulfonyl chloride or the like. An organic sulfonyl chloride, used for preparing the compound (1-3) with R4 being substituted or unsubstituted phenyl group, includes benzenesulfonyl chloride, p-toluenesulfonyl chloride or the like. The organic sulfonyl chloride may preferably be methanesulfonyl chloride or benzenesulfonyl chloride. 
The 2-amino-2xe2x80x2-diarylphosphino-1-1xe2x80x2-binaphthyl (1) of the invention forms a complex as its ligand with a transition metal. Such transition metal includes rhodium, ruthenium, iridium, nickel or the like. The complexes of the transition metals may be produced according to the known methods.
For example, the complex of rhodium may be synthesized by reacting the inventive 2-amino-2xe2x80x2-diarylphosphino-1-1xe2x80x2-binaphthyl (1) with bis(cycloocta-1,5-diene)rhodium (I) tetrafluoroborate, according the method described in xe2x80x9creviews on experimental chemistry: fourth edition xe2x80x9cvolume 18 xe2x80x9corganic metal complexxe2x80x9d pages 339 to 344 (edited by Japan Chemical society, published in 1991 by Maruzen). Such rhodium complexes include, for example, the followings.
Rh(L)Cl, Rh(L)Br, Rh(L)I,
[Rh(cod)(L)]BF4, [Rh(cod)(L)]ClO4,
[Rh(cod)(L)]PF6, [Rh(cod)(L)]BPh4,
[Rh(nbd)(L)]BF4, [Rh(nbd)(L)]ClO4,
[Rh(nbd)(L)]PF6, [Rh(nbd)(L)]BPh4 
(xe2x80x9ccodxe2x80x9d means 1,5-cyclooctadiene and xe2x80x9cnbdxe2x80x9d means norbornadiene)
The complex of ruthenium may be synthesized by heating and refluxing [Ru(cod)Cl2]n with MAP in the presence of triethylamine in toluene to react them with each other, according to the method described in a publication (J. Chem. Soc. Chem. Commun. 922 (1988)), or by heating and stirring [Ru(p-cymene)I2]2 with MAP in dichloromethane and ethanol, according to the method described in a publication (J. Chem. Soc. Chem. Commun. 1208 (1989)). Such ruthenium complexes include, for example, the followings.
Ru(OAc)2(L), Ru2Cl4(L)2NEt3,
[RuCl(benzene)(L)]Cl, [RuBr(benzene)(L)]Br, [RuI(benzene)(L)]I,
[RuCl(p-cymene)(L)]Cl, [RuBr(p-cymene)(L)]Br, [RuI(p-cymene)(L)]I,
[Ru(L)](BF4)2, [Ru(L)](ClO4)2, [Ru(L)](PF6)2, [Ru(L)](BPF4)2 
The complex of iridium may be prepared by reacting MAP with [Ir(cod)2xe2x80x2]BF4 in tetrahydrofuran with stirring, according to the method described in a publication (J. Chem. Soc. Chem. Commun. 1553 (1970)). Such iridium complexes include the followings.
Ir(L)Cl, Ir(L)Br, Ir(L)I,
[Ir(cod)(L)]BF4, [Ir(cod)(L)]ClO4,
[Ir(cod)(L)]PF6, [Ir(cod)(L)]BPh4,
[Ir(nbd)(L)]BF4, [Ir(nbd)(L)]ClO4,
[Ir(nbd)(L)]PF6, [Ir(nbd)(L)]BPh4 
The complex of nickel may be prepared according to the method described in xe2x80x9creviews on experimental chemistry: fourth edition xe2x80x9cvolume 18 xe2x80x9corganic metal complexxe2x80x9d page 376 (edited by Japan Chemical society, published in 1991 by Maruzen).
The complex of nickel may be prepared by dissolving MAP and nickel chloride in mixed solvent of isopropanol and methanol and heating the mixture with stirring, according to the method described in a publication (J. Am. Chem. Soc. 113, 9887, (1991)). Such nickel complexes include the followings.
NiCl2(L), NiBr2(L), NiI2(L)
The complexes of transition metals, having the opticallyl active aminophosphine compound MAP as the ligand, is useful as a catalyst for asymmetric hydrogenation. The complex may be used as a catalyst after or without purifying it.
Among the above complexes of transition metals, the complex containing iridium and the optically active aminophosphine compound SMAP as the ligand provides enantioselectivity higher than that of a complex of ruthenium containing BINAP, p-Tol-BINAP or the like as its ligand, when catalyzing asymmetric hydrogenation of geraniol. 
The asymmetric hydrogenation of geraniol, nerol and xcex3-geraniol using a ruthenium complex has already been reported (J. Am. Chem. Soc. 109, 1596, 4129 (1987); J. Organomet. Chem. 548, 65 (1997); Chem. Ind. (Dekker), 68, (1996)). When geraniol, nerol and xcex3-geraniol are subjected to asymmetric hydrogenation using the rhutenium complex of (S)-BINAP to produce citronellol, one of the enantiomers of citronellol is obtained when geraniol is hydrogenated and the other is obtained when nerol or xcex3-geraniol is hydrogenated. 
On the contrary, the asymmetric hydrogenation of either of geraniol, nerol or xcex3-geraniol using the iridium complex according to the invention provides only one of the enantiomers of citronellol, as shown in the following scheme 9. Therefore, even if the starting material of the asymmetric hydrogenation is a mixture of the trans-and cis-bodies of an allyl alcohol such as geraniol and nerol, the resulting product such as citronellol is composed of only one of its enantiomers. On the contrary, the above prior art using the ruthenium complex of (S)-BINAP inevitably produces a mixture of the enantiomers, when the starting material of the asymmetric hydrogenation is a mixture of geraniol and nerol. 
The inventive complex containing the 2-methylsulfonylamino-2xe2x80x2-diarylphosphino-1,1xe2x80x2-binaphthyl (SUMAP) as its ligand provides a high enantioselectivity in asymmetric carbon-carbon bond formation between norbornene and phenyl trifluoromethanesulfonate under the pressure of hydrogen. 
The inventive MAP may be used as a ligand of a complex of a transition metal. Such complex of a transition metal containing SMAP as its ligand is useful as a catalyst for asymmetric hydrogenation. In particular, its iridium complex provides enantioselectivity, as a catalyst for asymmetric hydrogenation of an allyl alcohol, higher than that of ruthenium complex containing BINAP or p-TolBINAP, and thus very useful in an industry. Further, the complex of 2-methylsulfonylamino-2xe2x80x2-diphenylphopsphino-1-1xe2x80x2-binaphthyl(SUMAP) provides a high enantioselectivity in asymmetric carbon-carbon bond formation between norbornene and phenyl trifluoromethanesulfonate. It is also possible to provide a compound with a desired absolute configuration in asymmetric sysnthesis, by using a complex of a transition metal having only one of (xe2x88x92)-and (+)-bodies of the inventive ligand as a catalyst for the asymmetric synthesis.